Nitrolysis of the CN Single Bond and Related Chemistry of Nitro and Nitroso Groups.
Annual rept. 1 Jan-31 Dec 83,
ILLINOIS UNIV AT CHICAGO CIRCLE
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Nitric acid in acetic anhydride converted N,N-dimethyl-benzylamine 1 to N-methyl-N-nitrosobenzylamine 2 76 and benzaldehyde. Six additional acyclic and alicyclic tertiary amines similarly gave nitrosamines 1,4-diazabicyclo 2,2,2 octane gave an intractable mixture. An explanation for the conversions is discussed. Addition of hydrocloric acid to the reaction mixture led to recovery of the amine 1 36, and to its conversion 54 to the nitrosamine 2 without the detectable formation of benzaldehyde in contrast nitric acid 100 and anhydrous hydrogen chloride in acetic anhydride converted the amine 1 to benzaldehyde 69 and to the nitrosamine 2 in low yield. Nitrosamine 2 and N-methyl-N-nitroso-Beta-phenethylamine 3 were oxidized to nitramines 4 and 5. It became desirable to incorporate alpha-functions into nitrosamines to provide schemes for the preparation of cage structure high energy materials. A proposed scheme is shown.
- Organic Chemistry